Magnetism in nanoclusters and cluster-assembled thin films

Increasing attention has been focused on the magnetic behavior of nanoparticles with diameters of 1-5 nm (approximately 50-5000 atoms). In this size range fundamental magnetic parameters such as the orbital and spin magnetic moments per atom deviate significantly from bulk values, and studying clusters addresses fundamental problems in mesoscopic magnetism, which is not as well understood as in either the atomic or the bulk regimes. There is also a growing realization of the enormous industrial potential of materials built by depositing preformed nanoclusters instead of atoms. If the clusters are size-selected and deposited in conjunction with an atomic vapor of a matrix material, it is possible to produce granular films in which there is independent control over the particle size and volume fraction. Using this technique, it also becomes possible to make granular mixtures of miscible materials. This unprecendented degree of control over the properties of the films holds the promise of new magnetic materials with "engineered properties." To fully realize this potential requires a greater understanding of not only the individual particles, but also how they interact in dense assemblies. There has been great progress in understanding some aspects of the magnetic behavior of nanoclusters and cluster-assembled materials. The mechanisms that generate spin and orbital moments that are enhanced by up to 36 and 200%, respectively, relative to the bulk in isolated clusters are well understood as is the dynamical behavior of the magnetic moment. Not so well understood is the observed magnetic anisotropy, which often has a different symmetry than the bulk. In dense assemblies, the nature of the interparticle coupling and the relative importance of dipolar and exchange interactions also require further research.     

Tuning of magnetic dipolar interactions of maghemite nanoparticles embedded in polyelectrolyte layer-by-layer films

In this study we report an experimental approach capable of tuning dipolar interactions in hybrid magnetic nanofilms produced via layer-by-layer assembly of positively-charged maghemite nanoparticles and sodium sulfonated polystyrene onto glass and silicon substrates. Morphological and magnetic properties of the as prepared nanofilms were determined by Raman spectroscopy, atomic force microscopy, conventional and SQUID magnetometry. Maghemite nanoparticles form densely packed layers with voids between particles being filled by polymeric material as observed in atomic force microscopy images. Magnetic hysteresis loops and zero-field-cooled/field-cooled magnetization curves reveal a superparamagnetic behavior at room temperature. The energy barrier for the magnetic moment reversal of the nanofilms has been determined from the frequency dependent ac susceptibility and is related to the gamma-Fe2O3 nanoparticles concentration used in the colloidal dispersion throughout film fabrication. Variations on the interparticle distances have a direct effect on the interparticle dipolar interactions. A less concentrated colloid gives rise to large separated nanoparticles inside the nanofilm with a consequent reduction on the energy barrier for the magnetic moment reversal. The fabrication process exploring the control of the nanoparticle concentration can thus be used to tune the magnetic dipolar interactions in the nanofilms.     

The effect of interactions on the saturation remanence of particulate assemblies

The effect of interactions on the saturation remanence of assemblies of identical, uniaxially anisotropic, single-domain particles is calculated using a spatial-mean interaction field. The particle easy-axis directions are assumed known and given by a distribution function. The remanence is determined by finding the magnetization orientation functional of the particle easy-axis orientation which minimizes the total assembly energy. Curves of remanence versus interaction strength (assembly packing fraction) are shown for a) randomly oriented assemblies of spherical particles with uniaxial crystalline anisotropy only, b) randomly oriented assemblies of acicular particles with shape anisotropy, and c) oriented assemblies of acicular particles with 6:1 aspect ratio. Disregarding external sample-shape demagnetization effects, this model always yields increased remanences due to interactions. A criterion is given which predicts when external shape effects are capable of dominating the net interaction field to yield a reduction in remanence. The applicability of these results and extensions of the theory are discussed in relation to particle assemblies in magnetic tape and high coercivity CoNiP films.     

Dipolar interaction effects in the magnetic and magnetotransport properties of ordered nanoparticle arrays

Assemblies of magnetic nanoparticles exhibit interesting physical properties arising from the competition of intraparticle dynamics and interparticle interactions. In ordered arrays of magnetic nanoparticles magnetostatic interparticle interactions introduce collective dynamics acting competitively to random anisotropy. Basic understanding, characterization and control of dipolar interaction effects in arrays of magnetic nanoparticles is an issue of central importance. To this end, numerical simulation techniques offer an indispensable tool. We report on Monte Carlo studies of the magnetic hysteresis and spin-dependent transport in thin films formed by ordered arrays of magnetic nanoparticles. Emphasis is given to the modifications of the single-particle behavior due to interparticle dipolar interactions as these arise in quantities of experimental interest, such as, the magnetization, the susceptibility and the magnetoresistance. We investigate the role of the structural parameters of an array (interparticle separation, number of stacked monolayers) and the role of the internal structure of the nanoparticles (single phase, core-shell). Dipolar interactions are responsible for anisotropic magnetic behavior between the in-plane and out-of-plane directions of the sample, which is reflected on the investigated magnetic properties (magnetization, transverse susceptibility and magnetoresistance) and the parameters of the array (remanent magnetization, coercive field, and blocking temperature). Our numerical results are compared to existing measurements on self-assembled arrays of Fe-based and Co nanoparticles is made.     

Properties of Dense Assemblies of Magnetic Nanoparticles Promising for Application in Biomedicine

Chemically synthesized iron oxide nanoparticles and magnetosomes produced by magnetotactic bacteria are of great importance for application in biomedicine. In this paper, we discuss the complicated magnetic anisotropy of the nanoparticles, the influence of the magnetostatic interactions, and thermal fluctuations on the behavior of these assemblies. Numerical simulation for dilute assemblies of iron oxide nanoparticles with combined magnetic anisotropy show that the uniaxial shape anisotropy dominates even for small aspect ratios of the particle, L/D≥1.1–1.2. The quasistatic hysteresis loops are calculated for various clusters of bacterial magnetosomes with diameters D=40–60 nm to understand the influence of magnetostatic interactions. The specific absorption rate (SAR) is calculated for assemblies of magnetic nanoparticles dispersed in solid and liquid media. A new electrodynamic method of measurement is used to obtain the SAR of the assembly of bacterial magnetosomes with average diameter D=48 nm.     

Self-Assembly of Magnetic Nanochains in an Intrinsic Magnetic Dipole Force-Dominated Regime

Magnetic nanoparticle chains offer the anisotropic magnetic properties that are often desirable for micro- and nanoscale systems; however, to date, large-scale fabrication of these nanochains is limited by the need for an external magnetic field during the synthesis. In this work, the unique self-assembly of nanoparticles into chains as a result of their intrinsic dipolar interactions only is examined. In particular, it is shown that in a high concentration reaction regime, the dipole–dipole coupling between two neighboring magnetic iron cobalt (FeCo) nanocubes, was significantly strengthened due to small separation between particles and their high magnetic moments. This dipole–dipole interaction enables the independent alignment and synthesis of magnetic FeCo nanochains without the assistance of any templates, surfactants, or even external magnetic field. Furthermore, the precursor concentration ([M] = 0.016, 0.021, 0.032, 0.048, 0.064, and 0.096 m ) that dictates the degree of dipole interaction is examined—a property dependent on particle size and inter-particle distance. By varying the spinner speed, it is demonstrated that the balance between magnetic dipole coupling and fluid dynamics can be used to understand the self-assembly process and control the final structural topology from that of dimers to linear chains (with aspect ratio >10:1) and even to branched networks. Simulations unveil the magnetic and fluid force landscapes that determine the individual nanoparticle interactions and provide a general insight into predicting the resulting nanochain morphology. This work uncovers the enormous potential of an intrinsic magnetic dipole-induced assembly, which is expected to open new doors for efficient fabrication of 1D magnetic materials, and the potential for more complex assemblies with further studies.     

Van der Waals versus dipolar forces controlling mesoscopic organizations of magnetic nanocrystals

The structure, thermodynamics and dynamics in many physical and chemical systems are determined by interplay of short-range isotropic and long-range anisotropic forces. Magnetic nanoparticles dispersed in solution are ideal model systems to study this interplay, as they are subjected to both isotropic van der Waals and anisotropic dipolar forces. Here we show from experiment an abrupt transition of maghemite nanocrystal organization from chain-like to random structures when nanoparticle solutions are evaporated under a magnetic field. This is explained by brownian dynamics simulations in terms of a variation of the strength of van der Waals interactions with the particle contact distance, which is tuned by the length of the molecules coating the particles. The weak dipole-dipole interactions between the maghemite particles are usually not sufficient to result in the chain formation observed here. However, due to the van der Waals interactions, when the nanocrystal contact distance is short enough, clusters of nanocrystals are formed during the evaporation process. These clusters exhibit large dipole moments compared with a single particle, which explains the formation of chain-like structures. Conversely, when the nanocrystal contact distance is too long, no nanocrystal aggregation occurs, and a random distribution of maghemite nanocrystals is obtained.     

Direct observation of dipolar chains in iron ferrofluids by cryogenic electron microscopy

A key issue in research on ferrofluids (dispersions of magnetic colloids) is the effect of dipolar interactions on their structure and phase behaviour, which is not only important for practical applications but gives fundamental insight in dipolar fluids in general. In 1970, de Gennes and Pincus predicted a Van der Waals-like phase diagram and the presence of linear chains of particles in ferrofluids in zero magnetic field. Despite many experimental studies, no direct evidence of the existence of linear chains of dipoles has been reported in the absence of magnetic field, although simulations clearly show the presence of chain-like structures. Here, we show in situ linear dipolar structures in ferrofluids in zero field, visualized on the particle level by electron cryo-microscopy on thin, vitrified films of organic dispersions of monodisperse metallic iron particles. On systematically increasing the particle size, we find an abrupt transition from separate particles to randomly oriented linear aggregates and branched chains or networks. When vitrified in a permanent magnetic field, these chains align and form thick elongated structures, indicating lateral attraction between parallel dipole chains. These findings show that the experimental model used is well suited to study the structural properties of dipolar particle systems.     

Improvement of the uniformity and dipole ferromagnetism in Co nanodots assemblies on Pb/Si(111) via step tuned dimensionality variation

We fabricated quasi-one-dimensional Co nanochain assemblies and two-dimensional Co nanodot assemblies on Pb/Si(111) substrates by step decoration. The morphology and magnetic properties of these two kinds of Co nanodot assemblies were investigated by in situ scanning tunneling microscopy and magneto-optical Kerr effect measurements. It was found that the steps cannot only improve the uniformity of the Co nanodots, but also increase the critical temperature T(c). Monte Carlo simulation indicates that the ferromagnetism mainly originates from the dipolar interactions and the critical temperature T(c) can be enhanced by introducing an in-plane uniaxial magnetic anisotropy via the step tuned dimensionality variation of the nanodot assemblies.     

DNA- and Field-Mediated Assembly of Magnetic Nanoparticles into High-Aspect Ratio Crystals

Under an applied magnetic field, superparamagnetic Fe₃O₄ nanoparticles with complementary DNA strands assemble into crystalline, pseudo-1D elongated superlattice structures. The assembly process is driven through a combination of DNA hybridization and particle dipolar coupling, a property dependent on particle composition, size, and interparticle distance. The DNA controls interparticle distance and crystal symmetry, while the magnetic field leads to anisotropic crystal growth. Increasing the dipole interaction between particles by increasing particle size or external field strength leads to a preference for a particular crystal morphology (e.g., rhombic dodecahedra, stacked clusters, and smooth rods). Molecular dynamics simulations show that an understanding of both DNA hybridization energetic and magnetic interactions is required to predict the resulting crystal morphology. Taken together, the data show that applied magnetic fields with magnetic nanoparticles can be deliberately used to access nanostructures beyond what is possible with DNA hybridization alone.     

Synthesis of ultrafine amorphous Fe–B alloy nanoparticles using anodic aluminum oxide templates

Ultrafine amorphous Fe–B alloy nanoparticles are self-assembled within anodic aluminum oxide templates by combining a preparation process of Fe–B nanoparticles with a template method. Scanning electron microscopy, inductively coupled plasma-atomic emission spectrometry, X-ray diffraction spectrometry, Mössbauer spectrometry, and vibrating sample magnetometry are employed to study the morphology, chemical composition, structure, and magnetic properties of the nanoparticle assemblies, respectively. The results show that the alloy particles are amorphous with a boron content of 24 at. % and can be in shape of sphere and rod by controlling the duration of preparation. There is a narrow distribution of the sizes of spherical nanoparticles with an average diameter below 35 nm in relatively short preparation time, while rods are found in longer time. The measurements of magnetic properties indicate that the nanoparticles are mostly in superparamagnetic state and the self-assembly of the nanoparticles has a weak magnetic anisotropy with an easy direction perpendicular to the template plane.     

Magnetic relaxation of gamma-Fe2O3 nanoparticles arrangements and electronic phase-segregated systems

Gamma-Fe2O3 nanoparticles have been synthesized and dispersed in a polymeric matrix, forming a series of composites with different concentrations of magnetic particles. The effect of volume polydispersity and dipolar interactions on the relaxation behavior is discussed. We have paid special attention to the dynamic approach to discuss a possible true superspin-glass transition in highly concentrated composites. To avoid the practical limitations that appear in highly concentrated systems of particles, like the formation of aggregates, etc., we have studied the glassy phase that appears spontaneously in certain strongly electronic correlated materials close to a metal-insulator transition. It must be emphasized that from a theoretical point of view these inhomogenous magnetic states could present important advantages over classical dispersions of particles, like field-control of the effective particle size. The results are compared with other recently obtained for classical systems of particles.     

Poly(methyl methacrylate) coating of soft magnetic amorphous and crystalline Fe,Co-B nanoparticles by chemical reduction

The structural and magnetic properties of a collection of nanoparticles coated by Poly(methyl methacrylate) through a wet chemical synthesis have been investigated. The particles display either an amorphous (M = Fe, Co) M-B arrangement or a mixed structure bcc-Fe and fcc-Co + amorphous M-B. Both show the presence of a metal oxi-hydroxide formed in aqueous reduction. The organic coating facilitates technological handling. The cost-effective synthesis involves a reduction in a Poly(methyl methacrylate) aqueous solution of iron(II) or cobalt(II) sulphates (< 0.5 M) by sodium borohydride (< 0.5 M). The particles present an oxidized component, as deduced from X-ray diffraction, M?ssbauer and Fe- and Co K-edge X-ray absorption spectroscopy and electron microscopy. For the ferrous alloys, this Fe-oxide is alpha-goethite, favoured by the aqueous solution. The Poly(methyl methacrylate) coating is confirmed by Fourier transform infrared spectroscopy. In pure amorphous core alloys there is a drastic change of the coercivity from bulk to around 30 Oe in the nanoparticles. The mixed structured alloys also lie in the soft magnetic regime. Magnetisation values at room temperature range around 100 emu/g. The coercivity stems from multidomain particles and their agglomeration, triggering the dipolar interactions.     

Hysteresis properties of sintered Sm Co5permanent magnets

The magnetic properties of individual SmCo5particles have been extensively studied in the literature. In the present work, initial magnetization curves and hysteresis loops of sintered SmCo5magnets have been drawn with a hysteresigraph. The observed properties depend on the previous magnetic treatment of the sample. After thermal demagnetization, the initial susceptibility is very high; after dc field demagnetization, it is very weak. The inner hysteresis loops are often unsymmetrical. Results are interpreted by considering the magnets as particle assemblies related together by dipolar interactions.     

静磁场下磁流变液微结构形态稳定性分析

作为磁偶极流体系统,磁流变液丰富的微结构形态及构成这些微结构的基本胞元决定了磁流变液在磁场-力场作用下的磁流变效应.对外加静磁场下具有单链、多链密排、正方、面心立方和体心立方胞元的微结构系统的磁势能进行了分析,结果表明具有体心立方胞元的微结构的平均磁势能较低,而具有正方胞元的微结构的平均磁势能较高.基于最小势能原理可知,静磁场下磁流变液中的颗粒容易形成具有体心立方胞元和多链密排胞元的微结构.     

The influence of polymer architecture on nanosized hydroxyapatite precipitation

In this work we present a facile way to produce hydroxyapatite (HAP) nanoparticles by wet chemical synthesis in the presence of polyelectrolytes under controlled temperature, pH, and atmospheric conditions. The resulting calcium rich carbonated HAP is sintered in an air atmosphere to investigate the thermal stability of the synthesized powders. The morphology and microstructure of the HAP nanoparticles were investigated by XRD, SEM, FTIR spectroscopy, thermal analysis, and particle size analyzer. Polyelectrolytes affect the coherent length of the crystalline domain, the dimension and particle size distribution of the crystals. The reduction in size is greater in the direction of the c-axis. The SEM micrograph shows the formation of well-crystallized, agglomerated small particles of HAP. The mean size of the subunit is smaller than that of the surface of the grain observed in SEM. X-ray analysis have shown that the resulting particles have high thermal stability.     

Surface modified superparamagnetic nanoparticles for drug delivery: Interaction studies with human fibroblasts in culture

The concept of drug delivery using magnetic nanoparticles greatly benefit from the fact that nanotechnology has developed to a stage that it makes possible not only to produce magnetic nanoparticles in a very narrow size distribution range with superparamagnetic properties but also to engineer particle surfaces to provide site specific delivery of drugs. The size and surface characteristics of the nanoparticles are crucial factors that determine the success of the particles when used in vivo. The aim of this study was to modify the surfaces of the magnetic nanoparticles with PEG to improve the biocompatibility of the nanoparticles by resisting protein adsorption and increasing their intracellular uptake. In this study, the poly(ethyleneglycol) (PEG) modified superparamagnetic iron oxide nanoparticles have been prepared and their influence on human dermal fibroblasts is assessed in terms of cell adhesion/viability, morphology, particle uptake and cytoskeletal organisation studies. Various techniques have been used to determine nanoparticle-cell interactions including light, fluorescence, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The modification of nanoparticle surface induced alterations in cell behaviour distinct from the unmodified particles, suggesting that cell response can be directed via specifically engineered particle surfaces.     

Nematic‐like Organization of Magnetic Mesogen‐Hybridized Nanoparticles

A fluid nematic‐like phase is induced in monodisperse iron oxide nanoparticles with a diameter of 3.3 nm. This supramolecular arrangement is governed by the covalent functionalization of the nanoparticle surface with cyanobiphenyl‐based ligands as mesogenic promoters. The design and synthesis of these hybrid materials and the study of their mesogenic properties are reported. In addition, the modifications of the magnetic properties of the hybridized nanoparticles are investigated as a function of the different grafted ligands. Owing to the rather large interparticular distances (about 7 nm), the dipolar interaction between nanoparticles is shown to play only a minor role. Conversely, the surface magnetic anisotropy of the particles is significantly affected by the surface derivatization.     

Phase Transformation and Magnetic Hardening in Isolated FePt Nanoparticles

Isolated monodisperse L1₀ FePt nanoparticles coated by carbon were obtained by adding enough surfactants that decomposed into carbon after the chemical synthesis and postannealing of the A1 FePt nanoparticles. The effect of isolation between FePt nanoparticles on the phase transition temperature and magnetic properties has been studied systematically by thermal, magnetic, and structural characterizations and analyses. It was found that the A1 to L1₀ phase transition temperature is dependent sensitively on the amount of isolation medium. The transition temperature shift reaches 150-200degC from nonisolated particle assemblies to completely isolated particles, which may be attributed to the high activation energy of the phase transformation for the isolated particles.     

Size-dependent magnetic properties of single-crystalline multiferroic BiFeO3 nanoparticles

As-prepared, single-crystalline bismuth ferrite nanoparticles show strong size-dependent magnetic properties that correlate with: (a) increased suppression of the known spiral spin structure (period length of approximately 62 nm) with decreasing nanoparticle size and (b) uncompensated spins and strain anisotropies at the surface. Zero-field-cooled and field-cooled magnetization curves exhibit spin-glass freezing behavior due to a complex interplay between finite size effects, interparticle interactions, and a random distribution of anisotropy axes in our nanoparticle assemblies.